The ozonolytic synthesis of acetophenone - a by-product for the production of drugs of calming effect
DOI:
https://doi.org/10.14739/2409-2932.2020.1.198119Keywords:
ozonolysis, ethylbenzene, acetophenone, acetic acid, oxidation, catalysis, ozoneAbstract
Acetophenone is an important by-product for the manufacture of drugs of calming effect. Known methods of its production don't have the future due to technological complexity, harsh synthesis conditions and low processing coefficients of raw materials. Therefore, the development of low-waste, low-temperature synthesis of acetophenone with ozone is an urgent task.
The purpose of the work was to study the kinetic regularities of the reaction of ozone with ethylbenzene in acetic acid and to create the ozonolytic synthesis of acetophenone.
Materials and methods. Glacial acetic acid of “Sigma” firm of qualification "Ch. P."; ethylbenzene, acetophenone of “Acros Organics” firm of qualification “Ch. P.”; acetates of metals of qualification “Ch. P.” were applied. The concentration of O3 in the gas phase was determined by a spectrophotometric absorption method in the range of 254–290 nm on spectrophotometer SF-46, which was designed to measure the transmittance of liquid and solid transparent substances in the spectral range from 190 to 1100 nm. Identification of the components of the reaction mass and their quantitative analysis in solution was performed by gas-liquid chromatography.
Results. The kinetic regularities of the oxidation of ethylbenzene with ozone in a solution of glacial acetate have been investigated. It is shown that ozone occurs at a temperature of 15 °C, mainly by the aromatic ring. The addition into the catalyst system - manganese (II) acetate has increased the selectivity of oxidation on the side chain from 34.0 to 87.7 %. Acetophenone (76.5 %) and methylphenylcarbinolacetate (11.2 %) are formed as the main products.
Conclusions. Ozonation of ethylbenzene in acetic acid was taken place mainly on the aromatic ring, and it was not possible to obtain acetophenone in high yield. The addition of transition metals allowed to be directed the process along the side ring to form 76 % acetophenone.
References
Pan, H. L., Li, S. T., Shu, M. J., Ye, Y. W., Cui, Q. H., & Zhao, Z. X. (2018). p-Xylene catalytic oxidation to terephthalic acid by ozone. Scienceasia, 44(3), 212-217. https://doi.org/10.2306/scienceasia1513-1874.2018.44.212
Chen, Y. H., Chang, C. Y., Chen, C. C., & Chiu, C. Y. (2006). Kinetics of ozonation of 2-mercaptothiazoline in an electroplating solution combined with UV radiation. Industrial & Engineering Chemistry Research, 45(14), 4936-4943. https://doi.org/10.1021/ie060065w
Galstyan, A., Galstyan, G., & Timoshyna, L. (2018). Research of the process of liquid phase selective oxidation of 4-aminotoluene with ozone. Chemistry & Chemical Technology, 12(3), 341-345. https://doi.org/10.23939/chcht12.03.341
Tarasenko, O. I., & Chalysh, I. A. (2010). Kinetyka ridynnofaznoho okysnennia hidroksytoluoliv ozonopovitrianoiu sumishshiu [Kinetics of liquid-phase oxidation of hydroxytoluenes by ozone-air mixture]. Ukrainskyi khimichnyi zhurnal, 76(1-2), 92-95. [in Ukrainian].
Ku, Y., Ji, Y. S., & Chen, H. W. (2008). Ozonation of o-cresol in aqueous solutions using a rotating packed-bed reactor. Water Environment Research, 80(1), 41-46. https://doi.org/10.2175/106143007x220905
Galstyan, G. A., Tyupalo, N. F., & Razumovskii S. D. (2004). Ozon i ego reaktsii s aromaticheskimi soedineniyami v zhidkoi faze [Ozone and its reactions with aromatic compounds in the liquid phase]. Lugansk: VNU. [in Russian].
Galstyan, G. A., Tyupalo, N. F., & Galstyan, A. G. (2009). Zhidkofaznoe kataliticheskoe okislenie aromaticheskikh soedinenii ozonom [Liquid-phase catalytic oxidation of aromatic compounds by ozone]. Lugansk: VNU. [in Russian].
Galstyan, G. A. (2017). Ozonolitychnyi syntez α-amino-α/-hidroksymetyl-4-nitroatsetofenonu [Ozonolysis of α-amino-α/-hydroxymethyl-4-nitroacetophenone in the liquid phase]. Current issues in pharmacy and medicine: science and practice, 10(1), 26-31. [in Ukrainian]. https://doi.org/10.14739/2409-2932.2017.1.93433
Kuleshova, T. S., & Galstyan, A. G. (2019). Ridynnofazne ozonuvannia etylbenzenu [Liquid-phase ozonation of ethylbenzene]. Voprosy Khimii i Khimicheskoi Tekhnologii, (3), 17-21. https://doi.org/10.32434/0321-4095-2019-124-3-17-21
Razumovskyi, S. D., Halstian, H. A., & Tiupalo, M. F. (2000). Ozon ta yoho reaktsii z alifatychnymy spolukamy [Ozone and its reactions with aliphatic compounds]. Luhansk: SUDU. [in Ukrainian].
Romanovskii, B. V. (2006). Osnovy khimicheskoi kinetiki [Fundamentals of chemical kinetics]. Moscow: Ekzamen. [in Russian].
Emanuel, N. M., Denisov, E. T., & Maizus, Z. K. (1965). Tsepnye reaktsii okisleniya uglevodov v zhidkoi faze [Chain reactions of oxidation of carbohydrates in the liquid phase]. Moscow: Nauka. [in Russian].
Potapenko, E. V., & Kudyukov, Yu. P. (2001). Okislenie 4-nitrotoluola ozonom v uksusnom angidride v prisutstvii sul`fata margancza [Oxidation of 4-nitrotoluene by ozone in acetic anhydride in the presence of manganese sulfate]. Kinetika i kataliz, 42(6), 1-4. [in Russian].
Galstjan, A. G., Bushuev, A. S., & Galstjan, T. M. (2010). Kataliticheskoe okislenie 3-atsetaminotoluola ozonovozdushnoi smes'yu v uksusnoi kislote [Catalytic oxidation of 3-acetaminotoluene by ozone-air mixture in acetic acid]. Vostochno-Evropeiskii zhurnal peredovykh tekhnologii, 1(6), 50-53. [in Russian].
Andreev, P. Y., Galstyan, A. G., & Galstyan, G. A. (2005). Oxidation of 2,4-dinitrotoluene with ozone in acetic acid in the presence of transition metal salts. Neftekhimiya, 45(5), 319-322.
Galstyan, A., Marshalok, H., Galstyan, T., Kuleshova, T., & Marshalok, O. (2019). Katalityczne utlenianie alkilobenzenów ozonem [Catalytic oxidation of alkylbenzenes with ozone]. Przemysł Chemiczny - Chemical Industry, 98(9), 1475-1478. [in Polish]. https://doi.org/10.15199/62.2019.9.30
Downloads
How to Cite
Issue
Section
License
Authors who publish with this journal agree to the following terms:
Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal. 
Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgement of its initial publication in this journal.
Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access)
